ABSTRACT
Mo(PMe(3))(6) cleaves a C-S bond of benzothiophene to give (kappa(2)-CHCHC(6)H(4)S)Mo(PMe(3))(4), which rapidly isomerizes to the olefin-thiophenolate and 1-metallacyclopropene-thiophenolate complexes, (kappa(1),eta(2)-CH(2)CHC(6)H(4)S)Mo(PMe(3))(3)(eta(2)-CH(2)PMe(2)) and (kappa(1),eta(2)-CH(2)CC(6)H(4)S)Mo(PMe(3))(4). The latter two molecules result from a series of hydrogen transfers and are differentiated according to whether the termini of the organic fragments coordinate as olefin or eta(2)-vinyl ligands, respectively. The reactions between Mo(PMe(3))(6) and selenophenes proceed differently from those of the corresponding thiophenes. For example, whereas Mo(PMe(3))(6) reacts with thiophene to give eta(5)-thiophene and butadiene-thiolate complexes, (eta(5)-C(4)H(4)S)Mo(PMe(3))(3) and (eta(5)-C(4)H(5)S)Mo(PMe(3))(2)(eta(2)-CH(2)PMe(2)), selenophene affords the metallacyclopentadiene complex [(kappa(2)-C(4)H(4))Mo(PMe(3))(3)(Se)](2)[Mo(PMe(3))(4)] in which the selenium has been completely abstracted from the selenophene moiety. Likewise, in addition to (kappa(1),eta(2)-CH(2)CC(6)H(4)Se)Mo(PMe(3))(4) and (kappa(1),eta(2)-CH(2)CHC(6)H(4)Se)Mo(PMe(3))(3)(eta(2)-CH(2)PMe(2)), which are counterparts of the species observed in the benzothiophene reaction, the reaction of Mo(PMe(3))(6) with benzoselenophene yields products resulting from C-C coupling, namely [kappa(2),eta(4)-Se(C(6)H(4))(CH)(4)(C(6)H(4))Se]Mo(PMe(3))(2) and [mu-Se(C(6)H(4))(CH)C(CH)(2)(C(6)H(4))](mu-Se)[Mo(PMe(3))(2)][Mo(PMe(3))(2)H].
ABSTRACT
Oxidative addition of H2 and D2 to the anthracene complex (eta6-AnH)Mo(PMe3)3 giving (eta4-AnH)Mo(PMe3)3X2 (X = H, D) is characterized by a normal equilibrium isotope effect (KH/KD > 1) at temperatures close to ambient; calculations on (eta4-AnH)Mo(PH3)3H2 indicate that this is a consequence of relatively low energy Mo-H vibrational modes.
Subject(s)
Anthracenes/chemistry , Hydrogen/chemistry , Molybdenum/chemistry , Organometallic Compounds/chemistry , Deuterium/chemistry , Molecular Conformation , Oxidation-Reduction , Stereoisomerism , TemperatureABSTRACT
In contrast to the benzene and naphthalene compounds (eta(6)-PhH)Mo(PMe(3))(3) and (eta(6)-NpH)Mo(PMe(3))(3), the anthracene complex (eta(6)-AnH)Mo(PMe(3))(3) reacts with H(2) to undergo a haptotropic shift and give the eta(4)-anthracene compound (eta(4)-AnH)Mo(PMe(3))(3)H(2). Density functional theory calculations indicate that the increased facility of naphthalene and anthracene to adopt eta(4)-coordination modes compared to that of benzene is a consequence of the fact that the Mo-(eta(4)-ArH) bonding interaction increases in the sequence benzene < naphthalene < anthracene, while the Mo-(eta(6)-ArH) bonding interaction follows the sequence benzene > naphthalene approximately anthracene.
ABSTRACT
The zinc thiolate complex [Tm(Ph)]ZnSCH2C(O)N(H)Ph, which features a tetrahedral [ZnS4] motif analogous to that of the Ada DNA repair protein, may be obtained by the reaction of Zn(NO3)2 with [Tm(Ph)]Li and Li[SCH2C(O)N(H)Ph] ([Tm(Ph)] = tris(2-mercapto-1-phenylimidazolyl)hydroborato ligand). Structural characterization of [Tm(Ph)]ZnSCH2C(O)N(H)Ph by X-ray diffraction demonstrates that the molecule exhibits an intramolecular N-H...S hydrogen bond between the amide N-H group and thiolate sulfur atom, a structure that is reproduced by density functional theory (DFT) calculations. The thiolate ligand of [Tm(Ph)]ZnSCH2C(O)N(H)Ph is subject to alkylation, a reaction that is analogous to the function of the Ada DNA repair protein. Specifically, [Tm(Ph)]ZnSCH2C(O)N(H)Ph reacts with MeI to yield PhN(H)C(O)CH2SMe and [Tm(Ph)]ZnI, a reaction which is characterized by second-order kinetics that is consistent with either (i) an associative mechanism or (ii) a stepwise dissociative mechanism in which the alkylation step is rate determining. Although the kinetics studies are incapable of distinguishing between these possibilities, a small normal kinetic isotope effect of kH/kD = 1.16(1) at 0 degrees C for the reaction of [Tm(Ph)]ZnSCH2C(O)N(H*)Ph (H* = H, D) with MeI is suggestive of a dissociative mechanism on the basis of DFT calculations. In particular, DFT calculations demonstrate that a normal kinetic isotope effect requires thiolate dissociation because it results in the formation of [PhN(H)C(O)CH2S]- which, as an anion, exhibits a stronger N-H...S hydrogen bonding interaction than that in [Tm(Ph)]ZnSCH2C(O)N(H)Ph. Correspondingly, mechanisms that involve direct alkylation of coordinated thiolate are predicted to be characterized by kH/kD < or = 1 because the reaction involves a reduction of the negative charge on sulfur and hence a weakening of the N-H...S hydrogen bonding interaction.
Subject(s)
Organometallic Compounds/chemical synthesis , Sulfhydryl Compounds/chemical synthesis , Zinc/chemistry , Alkylation , Crystallography, X-Ray , Hydrogen Bonding , Kinetics , Models, Molecular , Molecular Structure , Organometallic Compounds/chemistry , Sulfhydryl Compounds/chemistry , TemperatureABSTRACT
The molecular structure of the tris(2-mercapto-1-tolylimidazolyl)hydroborato complex [[Tm(p-Tol)]Zn(mim(p-Tol))][ClO(4)].3MeCN has been determined by X-ray diffraction, thereby demonstrating that the mim(p-Tol) ligand exhibits a N-H...O hydrogen bond with the [ClO(4)](-) counterion, [[Tm(p-Tol)]Zn(mim(p-Tol))...(OClO(3))], rather than hydrogen bond with a sulfur of the [Tm(p-Tol)] ligand. DFT calculations on a series of related complexes, namely [[Tm(Me)]Zn(mim(Me))](+), [[Tm(Me)]Zn(mim(Me))]...(OClO(3))], [[Tm(Me)]Zn(mim(Me))]...[O(H)Me]](+), and [[Tm(Me)]Zn(mim(Me))]...(NCMe)](+) demonstrate that an intramolecular N-H...S hydrogen bond within [[Tm(Me)]Zn(mim(Me))](+) is also less favored than the corresponding hydrogen bonding interactions with MeCN, MeOH, and [ClO(4)](-). The inability of the sulfur atoms of [Tm(R)] ligand to act as an effective hydrogen bond acceptor is in marked contrast to the ability of sulfur atoms in thiolate ligands to participate in the formation of N-H...S hydrogen bonds, an observation that reflects the "thione"versus"thiolate" nature of the [Tm(R)] ligand.
Subject(s)
Imidazoles/chemistry , Organometallic Compounds/chemistry , Crystallography, X-Ray , Hydrogen Bonding , Ligands , Models, Molecular , Molecular StructureABSTRACT
Experimental and computational studies on a series of cationic molybdenocene trihydride complexes, namely [Cp(2)MoH(3)]+, [(Cp(Bu)t)(2)MoH(3)]+, [Cp(2)MoH(3)]+, and ([Me(2)Si(C(5)Me(4))(2)]MoH(3))+, demonstrate that the most stable form for the ansa molybdenocene derivative is a nonclassical dihydrogen-hydride isomer, ([Me(2)Si(C(5)Me(4))(2)]Mo(eta(2)-H(2))(H))+, whereas the stable forms for the non-ansa complexes are classical trihydrides, [Cp(2)Mo(H)(3)]+, [(Cp(Bu)t)(2)Mo(H)(3)]+, and [Cp(2)Mo(H)(3)]+. In addition to altering the classical versus nonclassical nature of [Cp(2)MoH(3)]+ and ([Me(2)Si(C(5)Me(4))(2)]Mo(eta(2)-H(2))(H))+, the [Me(2)Si] ansa bridge also markedly influences the stability of the complex with respect to elimination of H(2) and dissociation of H+. Finally, computational studies on ([H(2)Si(C(5)H(4))(2)]MoH(2)D)+ and ([H(2)Si(C(5)H(4))(2)]MoHD(2))+ establish that deuterium exhibits a greater preference than hydrogen to occupy dihydrogen versus hydride sites.
ABSTRACT
The equilibrium isotope effect (EIE) for oxidative addition of H(2) and D(2) to Ir(PMe(2)Ph)(2)(CO)Cl has been measured over a large temperature range, thereby demonstrating that the inverse (<1) EIE previously observed at ambient temperature becomes normal (>1) at high temperature (>90 degrees C). The temperature dependence of the EIE for oxidative addition of H(2) and D(2) to Ir(PH(3))(2)(CO)Cl has been calculated using the geometry and vibrational frequencies obtained from DFT (B3LYP) calculations on Ir(PH(3))(2)(CO)ClH(2) and Ir(PH(3))(2)(CO)ClD(2), and is in accord with the experimentally observed transition from an inverse to normal EIE for oxidative addition of H(2) and D(2) to Ir(PMe(2)Ph)(2)(CO)Cl: the EIE is calculated to be inverse between 0 and 510 K, reach a maximum value of 1.15 at 867 K and then slowly decrease to unity as the temperature approaches infinity. This deviation from simple van't Hoff behavior, and the occurrence of a maximum in the EIE, is the result of the entropy term being temperature dependent. At low temperature, the enthalpy term dominates and the EIE is inverse, whereas at high temperatures the entropy term dominates and the EIE is normal. The observation of both normal and inverse EIEs for the same system indicate that inferences pertaining to the magnitude of an isotope effect at a single temperature may require more detailed consideration than previously realized.
ABSTRACT
The temperature dependence of the equilibrium isotope effects (EIEs) for coordination and oxidative addition of C-H and H-H bonds to the tungstenocene species {[H2Si(C5H4)2]W} has been determined with the aid of DFT (B3LYP) calculations. The EIE for coordination of CH4 and CD4 does not exhibit typical van't Hoff type behavior in which there is a monotonic variation of EIE with temperature; rather, the temperature dependence of the EIE exhibits a maximum, with inverse values (<1) at low temperature and normal values (>1) at high temperatures. The temperature dependence of the EIE for oxidative addition of CH4 and CD4 differs significantly from that for coordination, with the EIE being normal at all temperatures and approaching infinity at 0 K. In contrast to oxidative addition of methane which is normal at all temperatures, the EIE for oxidative addition of H2 and D2 exhibits a transition from inverse to normal upon raising the temperature. The existence of inverse EIEs in these systems at low temperatures is a result of the zero point energy changes for the products upon isotopic substitution being greater than those for the reactants (H2 or CH4).
ABSTRACT
Calculations on [H2Si(C5H4)2]W(Me)H demonstrate that the interconversion between [H2Si(C5H4)2]W(Me)H and the sigma-complex [H2Si(C5H4)2]W(sigma-HMe) is characterized by normal kinetic isotope effects for both reductive coupling and oxidative cleavage; the equilibrium isotope effect, however, is inverse and is the origin of the inverse kinetic isotope effect for the overall reductive elimination of methane.
ABSTRACT
The overall reductive elimination of RH from the ansa-molybdenocene and -tungstenocene complexes [Me(2)Si(C(5)Me(4))(2)]Mo(Ph)H and [Me(2)Si(C(5)Me(4))(2)]W(R)H (R = Me, Ph) is characterized by an inverse primary kinetic isotope effect (KIE) for the tungsten system but a normal KIE for the molybdenum system. Oxidative addition of PhH to [[Me(2)Si(C(5)Me(4))(2)]M] also differs for the two systems, with the molybdenum system exhibiting a substantial intermolecular KIE, while no effect is observed for the tungsten system. These differences in KIEs indicate a significant difference in the reactivity of the hydrocarbon adducts [Me(2)Si(C(5)Me(4))(2)]M(RH) for the molybdenum and tungsten systems. Specifically, oxidative cleavage of [Me(2)Si(C(5)Me(4))(2)]M(RH) is favored over RH dissociation for the tungsten system, whereas RH dissociation is favored for the molybdenum system. A kinetics analysis of the interconversion of [Me(2)Si(C(5)Me(4))(2)]W(CH(3))D and [Me(2)Si(C(5)Me(4))(2)]W(CH(2)D)H, accompanied by elimination of methane, provides evidence that the reductive coupling step in this system is characterized by a normal KIE. This observation demonstrates that the inverse KIE for overall reductive elimination is a result of an inverse equilibrium isotope effect (EIE) and is not a result of an inverse KIE for a single step. A previous report of an inverse kinetic isotope effect of 0.76 for C-H reductive coupling in the [Tp]Pt(CH(3))H(2) system is shown to be erroneous. Finally, a computational study provides evidence that the reductive coupling of [Me(2)Si(C(5)Me(4))(2)]W(Ph)H proceeds via the initial formation of a benzene sigma-complex, rather than an eta(2)-pi-benzene complex.
ABSTRACT
The reactions of Mo(PMe3)6 towards a variety of five- and six-membered heterocyclic nitrogen compounds (namely, pyrrole, indole, carbazole, pyridine, quinoline, and acridine) have been studied to provide structural models for the coordination of these heterocycles to the molybdenum centers of hydrodenitrogenation catalysts. Pyrrole reacts with Mo(PMe3)6 to yield the eta5-pyrrolyl derivative (eta5-pyr)Mo(PMe3)3H, while indole gives sequentially (eta1-indolyl)Mo(PMe3)4H, (eta5-indolyl)Mo(PMe3)3H, and (eta6-indolyl)Mo(PMe3)3H, with the latter representing the first example of a structurally characterized complex with an eta6-indolyl ligand. Likewise, carbazole reacts with Mo(PMe3)6 to give (eta6-carbazolyl)Mo(PMe3)3H with an eta6-carbazolyl ligand. The reactions of Mo(PMe3)6 with six-membered heterocyclic nitrogen compounds display interesting differences in the nature of the products. Thus, Mo(PMe3)6 reacts with pyridine to give an eta2-pyridyl derivative [eta2-(C5H4N)]Mo(PMe3)4H as a result of alpha-C-H bond cleavage, whereas quinoline and acridine give products of the type (eta6-ArH)Mo(PMe3)3 in which both ligands coordinate in an eta6-manner. For the reaction with quinoline, products with both carbocyclic and heterocyclic coordination modes are observed, namely [eta6-(C6)-quinoline]Mo(PMe3)3 and [eta6-(C5N)-quinoline]Mo(PMe3)3, whereas only carbocyclic coordination is observed for acridine.
ABSTRACT
Mo(PMe3)6 reacts with thiophene to give the eta5-thiophene complex (eta5-C4H4S)Mo(PMe3)3 and the eta5-butadiene-thiolate complex (eta5-C4H5S)Mo(PMe3)2(eta2-CH2PMe2), which are the first examples of (i) eta5-thiophene coordination and (ii) C-S cleavage and hydrogenation by a molybdenum compound. Deuterium labeling studies suggest that the hydrogenation of thiophene may involve an alkylidene intermediate, an observation that has ramifications for the mechanisms of hydrodesulfurization.